Fixative agents for hair

ABSTRACT

Hair-setting compositions comprising A) 0.5 to 20% by weight of a homopolymer of N-vinylcaprolactam or an anionic or nonionic copolymer of at least 70% by weight of N-vinylcaprolactam (polymer A), and B) 0.5 to 20% by weight of a terpolymer (polymer B) obtainable by copolymerization 
         (a) of at least one C 1 -C 4  N-alkylacrylamide or a C 1 -C 4  N-alkylmethacrylamide and    (b) at least one C 1 -C 4  hydroxyalkyl ester or a C 1 -C 4  alkyl ester of acrylic acid or methacrylic acid and (c) acrylic acid and/or methacrylic acid C) 0.5 to 20% by weight of a polymer chosen from the group consisting of copolymers of vinylpyrrolidone and a vinyl ester and of homopolymers of vinylpyrrolidone.

The present invention relates to novel hair-setting compositions whichcomprise polymer mixtures as film formers.

Hairspray compositions which consist of a polyester and a water-solublepolymer, for example a copolymer of N-vinylcaprolactam andN-vinylpyrrolidone, are known from WO 93/17658.

However, such hairsprays are moisture-sensitive and are therefore oflimited use with regard to application and handling.

EP 0 734 717 A2 describes hair-setting compositions comprising

-   -   A) 0.5 to 20% by weight of a homopolymer or copolymer of at        least 70% by weight of N-vinylcaprolactam (polymer A), and    -   B) 0.5 to 20% by weight of a further film-forming polymer        (polymer B) chosen from the group of polyamides, polyurethanes,        homopolymers and copolymers of monoolefinically unsaturated        monomers.

An unsatisfactory aspect of the hair-treatment compositions of the priorart is their stickiness.

It is an object of the present invention to develop hair-settingcompositions which have good setting properties coupled with goodability to be washed out without exhibiting the above-described moisturesensitivity and which are characterized by low stickiness.

We have found that this object is achieved by hair-setting compositionscomprising

-   -   A) 0.5 to 20% by weight of a homopolymer of N-vinylcaprolactam        or an anionic or nonionic copolymer of at least 70% by weight of        N-vinylcaprolactam (polymer A), and    -   B) 0.5 to 20% by weight of a terpolymer (polymer B) obtainable        by copolymerization        -   (a) of at least one C₁-C₄ N-alkylacrylamide or a C₁-C₄            N-alkylmethacrylamide and        -   (b) at least one C₁-C₄ hydroxyalkyl ester or a C₁-C₄ alkyl            ester of acrylic acid or methacrylic acid and        -   (c) acrylic acid and/or methacrylic acid    -   C) 0.5 to 20% by weight of a polymer chosen from the group        consisting of copolymers of vinylpyrrolidone and a vinyl ester        and of homopolymers of vinylpyrrolidone.

Suitable polymers A are homopolymers of N-vinylcaprolactam which areknown to the person skilled in the art and can be prepared, for example,in accordance with the procedure described in U.S. Pat. No. 3,145,147.These polymers are available under the tradename Luviskol® Plus (BASFAktiengesellschaft).

Further suitable polymers A are copolymers of N-vinylcaprolactam andfurther polymerizable monomers, where the copolymers consist of at least70% by weight, preferably at least 85% by weight, of N-vinylcaprolactam.

Suitable further polymerizable monomers for the copolymers A are:

-   -   monomers with an acid function, such as acrylic acid,        methacrylic acid, acrylamidomethylpropylsulfonic acid (AMPS),        3-sulfopropyl(meth)acrylate, optionally also in completely or        partially neutralized form;    -   C₁-C₁₈ alkyl(meth)acrylates, such as tert-butyl acrylate, ethyl        acrylate, isobutyl methacrylate, n-butyl methacrylate, methyl        methacrylate, ethyl methacrylate and hydroxyalkyl        (meth)acrylates;    -   vinyl esters of C₂-C₁₀ fatty acids, such as vinyl acetate, vinyl        propionate and vinyl esters of longer-chain and/or branched        fatty acids, for example versatic acid;    -   C₃-C₈ N-alkyl(meth)acrylamides, such as methacrylamide,        N,N-dimethylacrylamide, N-tert-butylacrylamide and        N-tert-octylacrylamide; N-vinylpyrrolidone and        N-vinylpiperidone.

The further monomers may be used in the form of an individual compoundor in the form of a mixture for the copolymer A.

Such copolymers are known and can be prepared by customarypolymerization processes.

For example, EP 455 081 describes copolymers of N-vinylpyrrolidone,N-vinylcaprolactam and N-vinylimidazole. EP 74191 discloses copolymersof N-vinylpyrrolidone, N-vinylcaprolactam and dimethylaminoethylmethacrylate.

For the hair-setting compositions according to the invention, preferenceis given to using homopolymers of N-vinylcaprolactam as polymers A.

The hair-setting compositions according to the invention comprise thepolymers A in an amount of from 0.5 to 20% by weight, preferably from 1to 10% by weight, based on the finished composition.

Suitable polymers B are terpolymers obtainable by copolymerization

-   -   (a) of at least one C₁-C₄ N-alkylacrylamide or a C₁-C₄        N-alkylmethacrylamide and    -   (b) at least one C₁-C₄ hydroxyalkyl ester or a C₁-C₄ alkyl ester        of acrylic acid or methacrylic acid and    -   (c) acrylic acid and/or methacrylic acid.

In a preferred embodiment, at least 50% of the carboxyl groups presentin the terpolymer have been neutralized with a lower organic base chosenfrom triethanolamine, triisopropanolamine,. 2-amino-2-methylpropanol and2-amino-2-methyl-1,3-propanediol.

The N-substituted acrylamides or methacrylamides which can be used asmonomers (a) are substituted by alkyl radicals which contain 1 to 4carbon atoms. Examples of such acrylamides and methacrylamides which canbe used are N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide,N-n-butylacrylamide, N-isopropylacrylamide, N-sec-butylacrylamide,N-tert-butylacrylamide, and the corresponding methacrylamides.Preference is given to the acrylamides and in particularN-tert-butylacrylamide.

Examples of alkylesters of acrylic acid or methacrylic acid which can beused as monomers (b) are methyl, ethyl, propyl, isopropyl or n-butylacrylate or methacrylate, preference being given to the acrylates overthe methacrylates. In this connection, particular preference is given toethyl acrylate. Furthermore, acrylates or methacrylates containinghydroxyl groups, such as, for example, hydroxyethyl acrylate,hydroxypropyl acrylate or hydroxyethyl methacrylate, can be used ascomponent (b).

A particularly preferred component (c) is acrylic acid.

Preference is given to polymers B) obtainable from

-   -   40 to 60% by weight of (a)    -   35 to 50% by weight of (b) and    -   3 to 11% by weight of (c)        based on the total weight of the monomer mixture—with the        proviso that the amounts add up to 100%.

A particularly preferred polymer B) is a terpolymer of acrylicacid/ethyl acrylate/N-tertiary-butylacrylamide. Such copolymers are soldunder the tradename Ultrahold® 8, Ultrahold Strong® (BASFAktiengesellschaft).

Suitable as polymer C) are homopolymers of N-vinylpyrrolidone, as aresold, for example, under the name Luviskol® from BASFAktiengesellschaft. The copolymers are obtainable by polymerization ofN-vinylpyrrolidone with vinyl acetate and/or vinyl propionate in variousweight ratios. Examples of such polymers are:

-   -   Luviskol® K17, Luviskol® K30, Luviskol® K60, Luviskol® K80,        Luviskol® K90 (polyvinylpyrrolidones with a corresponding K        value in the form of a powder or in the form of a solution        (aqueous or aqueous/alcoholic)).    -   Luviskol® VA=vinylpyrrolidone/vinyl acetate copolymers, in        particular Luviskol® VA 73, Luviskol® VA 64, Luviskol® VA 55,        Luviskol® VA 37.

In a particularly preferred embodiment, the hair-setting compositionscomprise

-   -   A) 0.5 to 20% by weight, in particular 1 to 5% by weight, based        on solid, of a homopolymer of N-vinylcaprolactam    -   B) 0.5 to 20% by weight, in particular 1 to 5% by weight, of a        terpolymer of N-tert-butylacrylamide, ethyl acrylate and acrylic        acid    -   C) 0.5 to 20% by weight, in particular 1 to 5% by weight, based        on solid, of a homopolymer of N-vinylpyrrolidone and/or a        copolymer of N-vinylpyrrolidone and vinyl acetate.

If they are made up of monomers containing acid groups, the polymers A,B and C can be used in the acid form or in partially or completelyneutralized form for the hair-setting compositions according to theinvention. Suitable agents for the neutralization are alkali metalhydroxides, ammonia, organic amines, in particular aminoalcohols, veryparticular preference being given to 2-amino-2-methyl-1-propanol.

The polymers A, B and C are present in a solvent, the solvents usedpreferably being water or alcohols or mixtures of water and loweralcohols. The solvent content in the hair-setting composition is usually25 to 98% by weight.

The mixing together of the polymers A, B and C can take place bydissolving A, B and C in the form of powders in a solvent, or by addingto a solution of one polymer, the other polymer in each case in the formof a solid or likewise in the form of a liquid.

The hair-setting compositions according to the invention comprise thepolymers B and C in an amount of from 0.5 to 20.0% by weight, preferablyfrom 1 to 5% by weight, based on the finished composition.

Besides the polymers A, B and C and a solvent, the hair-settingcompositions according to the invention can, depending on the intendeduse, comprise further customary hair cosmetic additives, such as perfumeoils, emulsifiers, preservatives, care substances, such as panthenol,silicone, collagen, vitamins, protein hydrolyzates, stabilizers, pHregulators, dyes, UV filters and further customary additives.

If the hair-setting composition according to the invention is to be usedin the form of a hairspray, then a propellant is usually added.Customary propellants are lower alkanes, for example propane or butane,dimethyl ether, nitrogen, nitrous oxide or carbon dioxide or mixtures ofthese substances. The hair-setting compositions according to theinvention can also comprise halogen-containing hydrocarbons aspropellant.

In the case of use in mechanical spray devices, for example spray pumps,the propellant can be dispensed with.

The hair-setting compositions according to the invention have excellentperformance properties; they form clear films and, in aqueous/alcoholicsolutions, have a low solution viscosity, meaning that even inrelatively high concentrations they still have good spray properties.Surprisingly, they exhibit a significantly reduced stickiness comparedwith known hair-setting compositions, in particular consisting ofvinylcaprolactam and/or vinylpyrrolidone and/or PVP/VA copolymer.

The polyvinylcaprolactam solutions used in the examples below were 40%strength by weight solutions in ethanol. The Fikentscher K value of thepolymer was 40 (1% in ethanol).

EXAMPLE 1

 7.5% by weight polyvinylcaprolactam solution  2.0% by weightUltrahold ® Strong (BASF Aktiengesellschaft)  1.5% by weightpolyvinylpyrrolidone (PVP) 89.0% by weight water, dist.

EXAMPLE 2

 7.5% by weight polyvinylcaprolactam solution  2.0% by weightUltrahold ® Strong (BASF Aktiengesellschaft)  1.5% by weightpolyvinylpyrrolidone (PVP) 65.0% by weight ethanol abs. 24.0% by weightwater, dist.

EXAMPLE 3

  5% by weight polyvinylcaprolactam solution  2.5% by weight Ultrahold ®8 (BASF Aktiengesellschaft)  2.5% by weight Luviskol ® K30 (BASFAktiengesellschaft): polyvinylpyrrolidone 90.0% by weight ethanol abs.

EXAMPLE 4

  5% by weight polyvinylcaprolactam solution  2.5% by weight Ultrahold ®8 (BASF Aktiengesellschaft)  2.5% by weight Luviskol ® K30 (BASFAktiengesellschaft): polyvinylpyrrolidone 90.0% by weight water, dist.

EXAMPLE 5

 5.0% by weight polyvinylcaprolactam solution  2.0% by weightUltrahold ® 8 (BASF Aktiengesellschaft)  2.5% by weight Luviskol ® VA64P, pulverulent copolymer of N-vinylpyrrolidone/vinyl acetate 52.5% byweight ethanol abs. 35.0% by weight water, dist.

EXAMPLE 6

   5% by weight polyvinylcaprolactam solution  2.5% by weightUltrahold ®, pulverulent terpolymer of N-tertiary-butylacrylamide, ethylacrylate, acrylic acid  1.5% by weight Luviskol ® K30 (BASFAktiengesellschaft): polyvinylpyrrolidone  0.23% by weight AMP 53.50% byweight ethanol abs. 37.27% by weight water, dist.

1. A hair-setting composition comprising A) 0.5 to 20% by weight of ahomopolymer of N-vinylcaprolactam or an anionic or nonionic copolymer ofat least 70% by weight of N-vinylcaprolactam (polymer A), and B) 0.5 to20% by weight of a terpolymer (polymer B) obtainable by copolymerization(a) of at least one C₁-C₄ N-alkylacrylamide or a C₁-C₄N-alkylmethacrylamide and (b) at least one C₁-C₄ hydroxyalkyl ester or aC₁-C₄ alkyl ester of acrylic acid or methacrylic acid and (c) acrylicacid and/or methacrylic acid C) 0.5 to 20% by weight of a polymer chosenfrom the group consisting of copolymers of vinylpyrrolidone and a vinylester and of homopolymers of vinylpyrrolidone.
 2. The hair-settingcomposition as claimed in claim 1, wherein a homopolymer ofN-vinylcaprolactam is used as polymer A.
 3. The hair-setting compositionas claimed in claim 1, wherein a terpolymer of N-tert-butylacrylamide,ethyl acrylate and acrylic acid is used as polymer B.
 4. The Ahair-setting composition as claimed in claim 1, further comprising analcohol and lower alkanes.
 5. The hair-setting composition as claimed inclaim 2, further comprising an alcohol and lower alkanes.
 6. Thehair-setting composition as claimed in claim 3, further comprising analcohol and lower alkanes.